Methods of fabricating plasticized, antiplasticized and crystalline conducting polymers and precursors thereof

ABSTRACT

Methods of forming materials containing precursors to electrically conductive polymers and electrically conductive polymers are described which have a high degree of crystallinity. The high degree of crystallinity is achieved by preparing the materials under conditions which provide a high degree of mobility to the polymer molecules permitting them to associate with one another to form a crystalline state. High levels of electrical conductivity are achieved in in the electrically conductive materials without stretch orienting the material. The enhanced electrical conductivity is isotropic as compared to a stretch oriented film which has isotropic electrical conductivity. In the preferred embodiment, additives are added to a solution containing a solvent and the precursor or electrically conductive polymer. The additives are preferably plasticizer of diluents. As the solvent is removed the material dries and contains a higher degree of crystallinity than in the absence of the additive.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority from Provisional Application Ser. No.60/007,688 filed Nov. 29, 1995.

U.S. patent application Ser. No. 08/620,619 entitled, "PLASTICIZED,ANTIPLASTICIZED AND CRYSTALLINE CONDUCTING POLYMERS AND PRECURSORSTHEREOF" and U.S. patent application Ser. No. 08/620,618 entitled,"POLYCRYSTALLINE CONDUCTING POLYMERS AND PRECURSORS THEREOF HAVINGADJUSTABLE MORPHOLOGY AND PROPERTIES", the teachings of which areincorporated herein by reference.

1. Field of the Invention

The present invention is directed to methods of fabricating crystallineelectrically conductive precursors and crystalline electricallyconductive polymers thereof and applications thereof.

2. Background

Electrically conductive organic polymers emerged in the 1970's as a newclass of electronic materials. These materials have the potential ofcombining the electronic and magnetic properties of metals with thelight weight, processing advantages, and physical and mechanicalproperties characteristic of conventional organic polymers. Examples ofelectrically conducting polymers are polyparaphenylene vinylenes,polyparaphenylenes, polyanilines, polythiophenes, polyazines,polyfuranes, polythianaphthenes polypyrroles, polyselenophenes,poly-p-phenylene sulfides, polyacetylenes formed from solubleprecursors, combinations thereof and blends thereof with other polymersand copolymers of the monomers thereof.

These polymers are conjugated systems which are made electricallyconducting by doping. The doping reaction can involve an oxidation, areduction, a protonation, an alkylation, etc. The non-doped ornon-conducting form of the polymer is referred to herein as theprecursor to the electrically conducting polymer. The doped orconducting form of the polymer is referred to herein as the conductingpolymer.

Conducting polymers have potential for a large number of applications insuch areas such as electrostatic charge/discharge (ESC/ESD) protection,electromagnetic interference (EMI) shielding, resists, electroplating,corrosion protection of metals, and ultimately metal replacements, i.e.wiring, plastic microcircuits, conducting pastes for variousinterconnection technologies (solder alternative), etc. Many of theabove applications especially those requiring high current capacity havenot yet been realized because the conductivity of the processibleconducting polymers is not yet adequate for such applications.

To date, polyacetylene exhibits the highest conductivity of all theconducting polymers. The reason for this is that polyacetylene can besynthesized in a highly crystalline form (crystallinity as high as 90%has been achieved) (as reported in Macromolecules, 25, 4106, 1992). Thishighly crystalline polyacetylene has a conductivity on the order of 10⁵S/cm. Although this conductivity is comparable to that of copper,polyacetylene is not technologically applicable because it is anon-soluble, non-processible, and environmentally unstable polymer.

The polyaniline class of conducting polymers has been shown to beprobably the most suited of such materials for commercial applications.Great strides have been made in making the material quite processable.It is environmentally stable and allows chemical flexibility which inturn allows tailoring of its properties. Polyaniline coatings have beendeveloped and commercialized for numerous applications. Devices andbatteries have also been constructed with this material. However, theconductivity of this class of polymers is generally on the low end ofthe metallic regime. The conductivity is on the order of 10⁰ S/cm. Someof the other soluble conducting polymers such as the polythiophenes,poly-para-phenylenevinylenes exhibit conductivity on the order of 10²S/cm. It is therefore desirable to increase the conductivity of thesoluble/processible conducting polymers, in particular the polyanilinematerials.

The conductivity (σ) is dependent on the number of carriers (n) set bythe doping level, the charge on the carriers (q) and on the interchainand intrachain mobility (μ) of the carriers.

σ=n q μ

Generally, n (the number of carriers) in these systems is maximized andthus, the conductivity is dependent on the mobility of the carriers. Toachieve higher conductivity, the mobility in these systems needs to beincreased. The mobility, in turn, depends on the morphology of thepolymer. The intrachain mobility depends on the degree of conjugationalong the chain, presence of defects, and on the chain conformation. Theinterchain mobility depends on the interchain interactions, theinterchain distance, the degree of crystallinity, etc. Increasing thecrystallinity results in increased conductivity as examplified bypolyacetylene. To date, it has proven quite difficult to attainpolyaniline in a highly crystalline state. Some crystallinity has beenachieved by stretch orientation or mechanical deformation (A. G.MacDiarmid et al in Synth. Met. 55-57, 753). In these stretch-orientedsystems, conductivity enhancements have been observed. The conductivityenhancement was generally that measured parallel to the stretchdirection. Therefore, the conductivity in these systems is anisotropic.It is desirable to achieve a method of controlling and tuning themorphology of polyaniline. It is desirable to achieve a method ofcontrolling and tuning the degree of crystallinity and the degree ofamorphous regions in polyaniline, which in turn provides a method oftuning the physical, mechanical, and electrical properties ofpolyaniline. It is further desirable to achieve highly crystalline andcrystalline polyaniline and to achieve this in a simple and usefulmanner in order to increase the mobility of the carriers and, therefore,the conductivity of the polymer. It is also further desirable to achieveisotropic conductivity, that is conductivity not dependent on directionas with stretch-oriented polyanilines.

OBJECTS

It is an object of the present invention to provide a method tofabricate electrically conducting polymer precursors and electricallyconducting polymers having adjustable morphology.

It is an object of the present invention to provide a method tofabricate electrically conducting polymer precursors and electricallyconducting polymers in which the degree of crystalline regions and thedegree of amorphous regions is adjustable.

It is an object of the present invention to provide a method tofabricate electrically conducting polymer precursors and electricallyconducting polymers having adjustable physical, mechanical, andelectrical properties.

It is an object of the present invention to provide a method tofabricate a crystalline electrically conducting polymer precursor andcrystalline conducting polymers.

It is another object of the present invention to provide a method tofabricate highly crystalline conducting polymer precursor andcrystalline conducting polymers.

It is another object of the present invention to provide a method tofabricate an electrically conducting polymer that exhibits enhancedcarrier mobility.

It is another object of the present invention to provide a method tofabricate an electrically conducting polymer which exhibits enhancedconductivity.

It is another object of the present invention to provide a method tofabricate an electrically conducting polymer which exhibits enhancedisotropic conductivity.

It is another object of the present invention to provide a method toinduce a plasticization effect in electrically conducting polymerprecursors and electrically conducting polymers.

It is another object of the present invention to provide a method tofabricate an antiplasticization effect in electrically conductingpolymer precursors and electrically conducting polymers.

It is another object of the present invention to add an additive to aprecursor or an electrically conductive polymer to induce enhancedmobility.

It is another object of the present invention to add an additive to aprecursor or an electrically conductive polymer to induce an enhanceddegree of crystallinity.

It is another object of the present invention to provide a method tofabricate a precursor or electrically conductive polymer which has anenhanced degree of crystallinity without being stretch oriented.

It is another object of the present invention to provide a method tofabricate a precursor or electrically conductive polymer which hasincreased glass transition temperature.

It is another object of the present invention to provide a method tofabricate a precursor or electrically conductive polymer which hasdecreased glass transition temperature.

It is another object of the present invention to provide a method tofabricate a precursor or electrically conductive polymer which hasenhanced mechanical properties.

It is another object of the present invention to provide a method tofabricate a precursor or electrically conductive polymer which hasdecreased mechanical properties.

SUMMARY OF THE INVENTION

A broad aspect of the present invention is a method of forming anadmixture of a solvent, an additive and a polymer selected from thegroup consisting of a precursor to an electrically conductive polymerand a electrically conductive polymer wherein the solvent is removed orpartially removed and the additive provides local mobility to thepolymer to allow the polymer chains to tightly associate with oneanother to achieve a high crystalline state.

In a more particular aspect of the present invention is a method offorming an admixture of a solvent, an additive and a polymer selectedfrom the group consisting of a precursor to an electrically conductivepolymer and an electrically conductive polymer wherein the solvent isremoved or partly removed and the additive provides a plasticizationeffect.

In a more particular aspect of the present invention is a method offorming an admixture of a solvent, an additive and a polymer selectedfrom the group consisting of a precursor to an electrically conductivepolymer and an electrically conductive polymer wherein the solvent isremoved or partly removed and the additive provides anantiplasticization effect.

BRIEF DESCRIPTION OF THE DRAWINGS

Further objects, features, and advantages of the present invention willbecome apparent from a consideration of the following detaileddescription of the invention when read in conjunction with the drawingsFIG's. in which:

FIG. 1 is a general formula for polyaniline in the non-doped orprecursor form.

FIG. 2 is a general formula for a doped conducting polyaniline.

FIG. 3 is a general formula for the polysemiquinone radical cation formof doped conducting polyaniline.

FIG. 4 is a Gel Permeation Chromatograph (GPC) of polyaniline base inNMP (0.1%). GPC shows a trimodal distribution--A very high molecularweight fraction (approx. 12%) and a major peak having lower molecularweight.

Curve 5(a) is a Wide Angle X-Ray Scattering (WAXS) spectrum for apolyaniline base film processed from NMP. The polymer film isessentially amorphous. Curve 5(b) is a Wide Angle X-Ray Scatteringspectrum for a polyaniline base film that has been stretch-oriented(1/lo=3.7). This film was derived from a gel. Curve 5(c) is a Wide AngleX-Ray Scattering spectrum for a polyaniline base film containing 10% ofpoly-co-dimethyl propylamine siloxane. This film is highly crystalline.

FIG. 6 is a Schematic diagram of a polycrystalline material as taught inpresent invention having crystalline regions (outlined in dottedrectangles) with intersticial amorphous regions.

FIG. 7 is a Dynamic Mechanical Thermal Analysis (DMTA) plot forpolyaniline base film cast from NMP. (First Thermal Scan; underNitrogen).

FIG. 8 is a DMTA plot which represents the second thermal scan for apolyaniline base film cast from NMP; This same film was previouslyscanned as shown in FIG. 7. Film Contains no residual solvent.

FIG. 9 is a DMTA plot for polyaniline base film cast from NMP andcontaining 5% poly-co-dimethyl aminopropyl siloxane (5% N content).First Thermal Scan.

FIG. 10 is a DMTA plot for polyaniline base film cast from NMP andcontaining 5% poly-co-dimethyl aminopropyl siloxane (5% N content).Second Thermal Scan (this same film was previously scanned as shown inFIG. 9) Film Contains no residual solvent.

FIG. 11 is a GPC for a polyaniline base solution in NMP containing 5%poly-co-dimethyl aminopropyl siloxane by weight to polyaniline. Thepolyaniline was 0.1% in NMP.

DETAILED DESCRIPTION

The present invention is directed toward electrically conducting polymerprecursors and conducting polymers having adjustable morphology and inturn adjustable physical, mechanical, and electrical properties. Thepresent invention is also directed toward controlling and enhancing the3-dimensional order or crystallinity of conducting polymer precursorsand of conducting polymers. In addition, the present invention isdirected towards enhancing the electrical conductivity of conductingpolymers. This is done by forming an admixture of an electricallyconducting polymer precursor or an electrically conducting polymer withan additive whereby the additive provides local mobility to themolecules so as to allow the conducting polymer precursor or conductingpolymer chains to associate with one another and achieve a highlycrystalline state. An example of such an additive is a plasticizer. Aplasticizer is a substance which when added to a polymer, solvates thepolymer and increases its flexibility, deformability, generallydecreases the glass transition temperature Tg, and generally reduces thetensile modulus. In certain cases, the addition of a plasticizer mayinduce antiplasticization, that is an increase in the modulus orstiffness of the polymer, an increase in Tg. Herein the additives canprovide a plasticization effect, an antiplasticization effect or botheffects.

Examples of polymers which can be used to practice the present inventionare of substituted and unsubstituted homopolymers and copolymers ofaniline, thiophene, pyrrole, p-phenylene sulfide, azines, selenophenes,furans, thianaphthenes, phenylene vinylene, etc. and the substituted andunsubstituted polymers, polyparaphenylenes, polyparaphenylevevinylenes,polyanilines, polyazines, polythiophenes, poly-p-phenylene sulfides,polyfuranes, polypyrroles, polythianaphthenes, polyselenophenes,polyacetylenes formed from soluble precursors and combinations thereofand copolymers of monomers thereof. The general formula for thesepolymers can be found in U.S. Pat. No. 5,198,153 to Angelopoulos et al.While the present invention will be described with reference to apreferred embodiment, it is not limited thereto. It will be readilyapparent to a person of skill in the art how to extend the teachingherein to other embodiments. One type of polymer which is useful topractice the present invention is a substituted or unsubstitutedpolyaniline or copolymers of polyaniline having general formula shown inFIG. 1 wherein each R can be H or any organic or inorganic radical; eachR can be the same or different; wherein each R¹ can be H or any organicor inorganic radical, each R¹ can be the same or different; x≧1;preferable x≧2 and y has a value from 0 to 1. Examples of organicradicals are alkyl or aryl radicals. Examples of inorganic radicals areSi and Ge. This list is exemplary only and not limiting. The mostpreferred embodiment is emeraldine base form of the polyaniline whereiny has a value of approximately 0.5. The base form is the non-doped formof the polymer. The non-doped form of polyaniline and the non-doped formof the other conducting polymers is herein referred to as theelectrically conducting polymer precursor.

In FIG. 2, polyaniline is shown doped with a dopant. In this form, thepolymer is in the conducting form. If the polyaniline base is exposed tocationic species QA, the nitrogen atoms of the imine (electron rich)part of the polymer becomes substituted with the Q+ cation to form anemeraldine salt as shown in FIG. 2. Q+ can be selected from H+ andorganic or inorganic cations, for example, an alkyl group or a metal.

QA can be a protic acid where Q is hydrogen. When a protic acid, HA, isused to dope the polyaniline, the nitrogen atoms of the imine part ofthe polyaniline are protonated. The emeraldine base form is greatlystabilized by resonance effects. The charges distribute through thenitrogen atoms and aromatic rings making the imine and amine nitrogensindistinguishable. The actual structure of the doped form is adelocalized polysemiquinone radical cation as shown in FIG. 3.

The emeraldine base form of polyaniline is soluble in various organicsolvents and in various aqueous acid solutions. Examples or organicsolvents are dimethylsulfoxide (DMSO), dimethylformamide (DMF) andN-methylpyrrolidinone (NMP), dimethylene propylene urea, tetramethylurea, pyridine, toluene, xylene, m-cresol, phenol, dimethylacetamide,n-cyclohexylpyrrolidinone, aqueous acetic acid, aqueous formic acid,pyrrolidinone, N,N' dimethyl propylene urea (DMPU), benzyl alcohol andwater, etc. This list is exemplary only and not limiting.

Examples of aqueous acid solutions is 80% acetic acid and 60-88% formicacid. This list is exemplary only and not limiting.

Polyaniline base is generally processed by dissolving the polymer inNMP. These solutions exhibit a bimodal or trimodal distribution in GelPermeation Chromatography (GPC) as a result of aggregation induced byinternal hydrogen bonding between chains as previously described in U.S.patent application Ser. No. 08/370,128, filed on Jan. 9, 1995, theteaching of which is incorporated herein by reference. The GPC curve fortypical polyaniline base in NMP is shown in FIG. 4.

Polymers in general can be amorphous, crystalline, or partlycrystalline. In the latter case, the polymer consists of crystallinephases and amorphous phases. The morphology of a polymer is veryimportant in determining the polymer's physical, mechanical, andelectronic properties.

Polyaniline base films processed from NMP either by spin-coating or bysolution casting techniques are amorphous as can be seen in FIG. 5awhich depicts the Wide Angle X-Ray Scattering (WAXS) spectrum for thismaterial. Amorphous diffuse scattering is observed. Some crystallinityis induced in these films by post processing mechanical deformationespecially if these films are derived from gels as described by A. G.MacDiarmid et al in Synth. Met. 55-57, 753 (1993). WAXS of a stretchoriented film having been stretched (1/lo=3.7X) derived from a gel isshown in FIG. 5b. Some crystallinity has been induced as compared to thenon-stretch oriented films as evidenced by the defined scattering peaks.

Doping the amorphous polyaniline base films (those having structureshown in FIG. 5a) with aqueous hydrochloric acid results in isotropicconductivity of 1 S/cm. Such films are not crystalline. Similar dopingof stretch oriented films results in anisotropic conductivity whereconductivity on the order of 10² S/cm is measured parallel to thestretch direction whereas conductivity on the order of 10⁰ S/cm ismeasured perpendicular to the stretch direction. It should also be notedthat some level of crystallinity is lost during the doping process inthese films.

According to the present invention, the interchain (polymer chain)registration is increased as compared to a stretch oriented film.

FIGS. 7 and 8 show the dynamic mechanical thermal analysis (DMTA)spectrum for a polyaniline base film processed from NMP alone. FIG. 7 isthe first scan where a Tg of approx. 118 is observed as a result of theresidual NMP which is present in the film. FIG. 8 is the second thermalscan of the same film. This film has no residual solvent and a Tg of≅251° C. is measured for the polyaniline base polymer.

When an additive such as a plasticizer, such as a poly-co-dimethylpropylamine siloxane, is added to the polyaniline base completelydifferent properties and morphology is observed. The siloxane has apolar amine group which facilitates the miscibility of the polyanilinebase and the plasticizer. The DMTA of a polyaniline base film cast fromNMP and containing 5% by weight to polyaniline of the poly-co-dimethylpropyl amine siloxane exhibits a lower Tg on the first thermal scan ascompared to polyaniline base processed from NMP alone (FIG. 9) as aresult of plasticization induced by the siloxane. However, on the secondthermal scan of this film (FIG. 10), the polymer exhibits an increase inTg as compared to polyaniline processed from NMP. When the polysiloxaneis added to a solution of polyaniline base, the siloxane due to thepolar amine group can interact with the polymer chains and disrupt someof the polyaniline interactions with itself or some of the aggregation.Thus, the polysiloxane first induces some deaggregation. However, thepolysiloxane has multiple amine sites and thus, it can itself hydrogenbond with multiple polyaniline base chains and thus, the polysiloxanefacilitates the formation of a cross-linked network. This cross-linkednetwork accounts for the increased Tg observed in the DMTA. Tg ischaracteristic of the amorphous regions of a polymer and in this casethe amorphous regions consist of a cross-linked polyaniline/polysiloxanenetwork. Thus, the polysiloxane is inducing an antiplasticization effectin polyaniline base as the Tg is increased. Generally, plasticizersreduce Tg. GPC data (FIG. 11) is consistent with this model. Theaddition of the poly-amino containing siloxane to a polyaniline basesolution in NMP results in a significant increase in the high molecularweight fractions depicting the cross-linked network which forms betweenpolyaniline and the plasticizer.

In addition to the cross-linked network the siloxane induces in theamorphous regions, concomittantly it also is found to induce significantlevels of crystallinity in polyaniline base as a result of the localmobility that it provides. FIG. 5c shows the WAXS for a polyaniline basefilm processed from NMP containing 10% of the poly amino containingsiloxane. As can be seen highly crystalline polyaniline has beenattained. Much higher levels of crystallinity as compared to FIG. 5b forthe stretch oriented films.

Thus polyaniline by the addition of the siloxane forms a structuredepicted in FIG. 6 where crystalline regions of highly associatedpolyaniline chains (outlined by a rectangle) are formed withintersticial amorphous regions. In most cases, the additive resides inthe amorphous intersticial sites. The degree of crystallinity (number ofcrystalline sites) and the size of the crystalline domains as well asthe degree of amorphous regions and the nature of the amorphous region(aggregated, i.e. cross-linked or not) can be tuned by the type andamount of additive. In turn, by controlling the above, the properties ofthe material can also be controlled.

With the poly-co-dimethyl aminopropyl siloxane (5% N content), loadingsranging from 0.001 to 20 % by weight gives highly crystallinepolyaniline. The highly crystalline polyaniline in turn exhibitsincreased modulus, stiffness, yield and tensile strengths, hardness,density and softening points. Thus, the siloxane at these loadings ishaving an antiplasticization effect. Above 20% loading, thecrystallinity begins to decrease. As the crystallinity decreases, themodulus, stiffness, yield and tensile strengths, hardness, density andsoftening points begin to decrease. Thus, the siloxane at these loadingsbegins to have a plasticization effect. The siloxane content becomeshigh enough that it disrupts the polyaniline base interactions in thecrystalline regions. With the poly co dimethyl aminopropyl siloxaneshaving 0.5 and 13% N ratios, similar trends are observed but theparticular amount of siloxane needed to have a plasticization effect oran antiplasticization effect varies. Thus, the degree of crystallinityand the degree of amorphous regions and in turn the properties ofpolyaniline can be tuned by the nature of the additive as well as theamount of additive. Indeed, using the same additive but simply changingthe loading dramatically changes the morphology and in turn theproperties of polyaniline.

The electronic properties of the polymer are also impacted. Theconductivity of a polyaniline base film cast from NMP and containing 1%by weight poly-co-dimethyl aminopropyl siloxane which is doped byaqueous hydrochloric acid is 50 S/cm as compared to 1 S/cm for apolyaniline film with no plasticizer. This is isotropic conductivity.The doped film containing the polysiloxane retains the highlycrystalline structure.

The degree of crystallinity and the degree of amorphous regions and inturn the physical, mechanical, and electronic properties can be tuned bythe particular additive used and by the amount of additive. For example,the Tg of polyaniline can be increased or decreased by the amount andtype of additive. The mechanical properties such as tensile properties,modulus, impact resistance, etc. can be tuned as described above. Theadditive can range from 0.001 to 90% by weight, more preferably from0.001 to 50% and most preferably from 0.001 to 25%. A list ofplasticizers that can be used to practice the present invention is givenin Table 1. The plasticizer can be small molecules, oligomeric orpolymeric in nature as can be seen in Table 1. They can bemonofuntional, bifunctional, and multifunctional. The additive can alsobe removed from the final film structure if so desired by appropriateextraction.

SPECIFIC EXAMPLES

Polyaniline Synthesis

Polyaniline is synthesized by the oxidative polymerization of anilineusing ammonium peroxydisulfate in aqueous hydrochloric acid. Thepolyaniline hydrochloride precipitates from solution. The polymer isthen neutralized using aquoeous ammonium hydroxide. The neutralized ornon-dope polyaniline base is then filtered, washed and dried.Polyaniline can also be made by electrochemical oxidative polymerizationas taught by W. Huang, B. Humphrey, and A. G. MacDiarmid, J. Chem. Soc.,Faraday Trans. 1, 82, 2385, 1986.

Polyaniline Base in NMP

The polyaniline base powder is readily dissolved in NMP up to 5% solids.Thin films (on the order of a micron) can be formed by spin-coating.Thick films are made by solution casting and drying (70° C. in vacuumoven under a nitrogen purge for 15 hours). These solutions and filmshave the properties described above.

Polyaniline Base in NMP/Plasticizer

a. Polyaniline Base was first dissolved in NMP to 5% solids and allowedto mix well. A poly-co-dimethyl, aminopropyl siloxane (N content 5%relative to repeat unit) was dissolved to 5% in NMP. The siloxanesolution was added to the polyaniline base solution. The resultingadmixture was allowed to mix for 12 hours at room temperature. A numberof solutions were made having from 0.001 % to 50% siloxane content (byweight relative to polyaniline). Thin films were spin-coated onto quartzsubstrates; Thick films were prepared by solution casting and baking thesolutions at 70° C. in a vacuum oven under a Nitrogen purge for 15hours). The solutions and the films have the properties described above.

b. The same experiment described in (a) was carried out except that theplasticizer was a poly-co-dimethyl, aminopropyl siloxane in which the Ncontent was 13%.

c. The same experiment described in (a) was carried out except that theplasticizer was a poly-co-dimethyl, aminopropyl siloxane in which the Ncontent was 0.5%.

d. The same experiment described in (a) was carried out except that theplasticizer was polyglycol diacid.

e. The same experiment described in (a) was carried out except that theplasticizer was 3,6,9-trioxaundecanedioic acid.

f. The same experiment described in (a) was carried out except that theplasticizer was poly(ethylene glycol) tetrahydro furfuryl ether.

g. The same experiment described in (a) was carried out except that theplasticizer was glycerol triacetate.

h. The same experiment described on (a) was carried out except theplasticizer was epoxidized soy bean oil.

Polyaniline Base in NMP/m-Cresol/Plasticizer

The same experiment as described in (a) was carried out except thatpolyaniline base and the plasticizer was dissolved in NMP/m-Cresolmixtures in which m-Cresol ranged from 1 to 99%

Polyaniline Base in m-Cresol/Plasticizer

The same experiment as described in (a) was carried out except that thepolyaniline base was dissolved in m-Cresol and the plasticizer wasdissolved in m-Cresol.

Polyaniline Base in m-Cresol and in NMP/m-Cresol

Polyaniline Base was dissolved in m-Cresol and in NMP/m-Cresolcombinations to 5% solids. The m-Cresol in the latter system being theadditive ranged from 1 to 99%. Free-Standing films were made by solutioncasting techniques. With increasing m-cresol content, the polyanilineexhibited a WAXS similar to that shown in FIG. 5a except that theamorphous scattering peak became somewhat sharper indicative of somecrystallinity. However, this was significantly less than observed withthe siloxane plasticizer.

Doped Polyanilines

1. Hydrochloric Acid and/or Methanesulfonic Acid Doped Films

Polyaniline base films made as described above were doped by aqueousacid solutions of hydrochloric or methanesulfonic acid. The films wereimmersed in the acid solution for 12 hours for thin films and 36 hoursfor the thick films. The conductivity of a polyaniline base filmprocessed from NMP and doped with these acid solutions is 1 S/cm. Theconductivity of a base film processed from NMP and 1% poly-co-dimethyl,aminopropyl siloxane (5% N content) was 50 S/cm.

2. Sulfonic Acid Doped Polyanilines

Polyaniline Base was dissolved in a solvent such as NMP or NMP/m-Cresolcombinations, etc. from 1 to 5% solids. To this solution was added adopant such as camphorsulfonic acid or acrylamidopropanesulfonic acid(previously reported in U.S. patent application Ser. No. 595,853 filedon Feb. 2, 1996). These solutions were used to spin-coat or solutioncast films. In some experiments, the plasticizer such as thepoly-co-dimethyl, aminopropyl siloxane in a solvent was added to thedoped polyaniline solution. In certain other experiments, theplasticizer was first added to the pani base solution. The dopant wasthen added to the polyaniline solution containing the plasticizer.

The teaching of the following U.S. Patent Applications are incorporatedherein by reference:

"CROSS-LINKED ELECTRICALLY CONDUCTIVE POLYMERS, PRECURSORS THEREOF ANDAPPLICATIONS THEREOF", application Ser. No. 595,853, filed Feb. 2, 1996;

"METHODS OF FABRICATION OF CROSS-LINKED ELECTRICALLY CONDUCTIVE POLYMERSAND PRECURSORS THEREOF", application Ser. No. 594,680, filed Feb. 2,1996;

"DEAGGREGATED ELECTRICALLY CONDUCTIVE POLYMERS AND PRECURSORS THEREOF",application Ser. No.370,127, filed Jan. 9, 1995; and

"METHODS OF FABRICATION OD DEAGGREGATED ELECTRICALLY CONDUCTIVE POLYMERSAND PRECURSORS THEREOF", application Ser. No. 370,128, filed Jan. 9,1995.

While the present invention has been shown and described with respect toa preferred embodiment, it will be understood that numerous changes,modifications, and improvements will occur to those skilled in the artwithout departing from the spirit and scope of the invention.

                  TABLE I                                                         ______________________________________                                        PLASTICIZERS                                                                  OIPIC ACID DERIVATIVES                                                        Dicapryl adipate                                                              Di-(2-ethylhexyl adipate                                                      Di(n-heptyl, n-nonyl) adipate                                                 Diisobutyl adipate                                                            Diisodecyl adipate                                                            Dinomyl adipate                                                               Di-(tridecyl) adipate                                                         ZELAIC ACID DERIVATIVES                                                       Di-(2-ethylheyl azelate)                                                      Diisodecyl azelate                                                            Diisoctyl azelate                                                             Dimethyl azelate                                                              Di-n-hexyl azelate                                                            ENZOIC ACID DERIVATIVES                                                       Diethylene glycol dibenzoate                                                  Dipropylene glycol dibenzoate                                                 Polyethylene glycol 200 dibenzo                                               TRIC ACID DERIVATIVES                                                         Acetyl tri-n-butyl citrate                                                    Acetyl triethyl citrate                                                       Tri-n-butyl citrate                                                           Triethyl citrate                                                              MER ACID DERIVATIVES                                                          Bis-(2-hydroxyethyl dimerate)                                                 OXY DERIVATIVES                                                               Epoxidized linseed oil                                                        Epoxidized soy bean oil                                                       2-Ethylhexyl epoxytallate                                                     n-Octyl epoxystearate                                                         MARIC ACID DERIVATIVES                                                        Dibutyl fumarate                                                              LCEROL DERIVATIVES                                                            Glycerol triacetate                                                           OBUTYRATE DERIVATIVE                                                          2,2,4-Trimethyl-1,3-pentanediol,                                              Diisobutyrate                                                                 ISOPHTHALIC ACID DERIVATIVES                                                  Di-(2-ethylhexyl) isophthalate                                                Dimethyl isophthalate                                                         Diphenyl isophthalate                                                         LAURIC ACID DERIVATIVES                                                       Methyl laurate                                                                LINOLEIC ACID DERIVATIVE                                                      Methyl linoleate, 75%                                                         MALEIC ACID DERIVATIVES                                                       Di-(2-ethylhexyl) maleate                                                     Di-n-butyl maleate                                                            MELLITATES                                                                    Tricapryl trimellitate                                                        Tri-(2-ethylhexyl) trimellitate                                               Triisodecyl trimellitate                                                      Tri-(n-octyl,n-decyl) trimellitate                                            MYRISTIC ACID DERIVATIVES                                                     Isopropyl myristate                                                           OLEIC ACID DERIVATIVES                                                        Butyl oleate                                                                  Glycerol monooleate                                                           Glycerol trioleate                                                            Methyl oleate                                                                 n-Propyl oleate                                                               Tetrahydrofurfuryl oleate                                                     PALMITIC ACID DERIVATIVES                                                     Isopropyl palmitate                                                           Methyl palmitate                                                              PARAFFIN DERIVATIVES                                                          Chloroparaffin, 41% Cl                                                        Chloroparaffin, 50% Cl                                                        Chloroparaffin, 60% Cl                                                        Chloroparaffin, 70% Cl                                                        PHOSPHORIC ACID DERIVATIVES                                                   2-Ethylhexyl diphenyl phosphate                                               Isodecyl diphenyl phosphate                                                   t-Butylphenyl diphenyl phosphate                                              Tri-butoxyethyl phosphate                                                     Tributyl phosphate                                                            Tricresyl phosphate                                                           Triphenyl phosphate                                                           PHTHALIC ACID DERIVATIVES                                                     Butyl benzyl phthalate                                                        Butyl octyl phthalate                                                         Dicapryl phthalate                                                            Dicyclohexyl phthalate                                                        Di-(2-ethylhexyl) phthalate                                                   Diethyl phthalate                                                             Dihexyl phthalate                                                             Diisobutyl phthalate                                                          Diisodecyl phthalate                                                          Diisononyl phthalate                                                          Diisooctyl phthalate                                                          Dimethyl phthalate                                                            Ditridecyl phthalate                                                          Diundecyl phthalate                                                           RICINOLEIC ACID DERIVATIVES                                                   Butyl ricinoleate                                                             Glyceryl tri(acetyl) ricinoleate)                                             Methyl acetyl ricinoleate                                                     Methyl ricinoleate                                                            n-Butyl acetyl ricinoleate                                                    Propylene glycol ricinoleate                                                  SEBACIC ACID DERIVATIVES                                                      Dibutyl sebacate                                                              Di-(2-ethylhexyl) sebacate                                                    Dimethyl sebacate                                                             STEARIC ACID DERIVATIVES                                                      Ethylene glycol monostearate                                                  Glycerol monostearate                                                         Isopropyl isostearate                                                         Methyl stearate                                                               n-Butyl stearate                                                              Propylene glycol monostearate                                                 SUCCINIC ACID DERIVATIVES                                                     Diethyl succinate                                                             SULFONIC ACID DERIVATIVES                                                     N-Ethyl o,p-toluenesulfonamide                                                o,p-toluenesulfonanamide                                                      Polyesters                                                                    adipic acid polyester                                                         Paraplex G-40                                                                 adipic acid polyester                                                         Santicizer 334F                                                               azelaic acid polyester                                                        Plastolein 9720)                                                              azelaic acid polyester                                                        Plastolein 9750                                                               sebacic acid polyester                                                        Paraplex G-25                                                                 Sucrose derivatives                                                           sucrose acetate-isobutyrate (SAIB)                                            Tartaric acid derivative                                                      dibutyl tartrate                                                              Terephthalic acid derivative                                                  bis(2-ethylhexyl) terephthalate                                               (DOTP)                                                                        Trimellitic acid derivatives                                                  tris(2-ethylhexyl) trimellitate                                               (TOTM)                                                                        heptyl nonyl trimellitate                                                     heptyl nonyl undecyl trimellitate                                             triisodecyl trimellitate                                                      Glycol derivatives                                                            diethylene glycol dipolargonaic                                               triethylene glycol di-2                                                       ethylbutyrate                                                                 poly(ethylene glycol) (200) di 2-                                             ethylhexanoate                                                                Glycolates                                                                    methyl phthalyl ethyl glycolnic                                               butyl phthalyl butyl glycolnic                                                Hydrocarbons                                                                  hydrogenated terphenyls HR-40                                                 poly(alkyl naphthalene)s Panaflex                                             aliphatic aromatics Leromoll                                                  chlorinated paraffin (52 wt % Cl),                                            Cereclor S-52                                                                 Terpenes and Derivatives                                                      Camphor                                                                       Hydrogenated methyl ester or rosin                                            Phosphonic Acid Derivatives                                                   Chlorinated Polyphosphanate                                                   Siloxanes                                                                     Polydimethyl siloxane                                                         Polyco-dimethyl/propylamine siloxanes with various amount of                  propylamine content                                                           Polydiphenyl siloxanes                                                        Polyco-dimethylphenyl siloxanes                                               Silanol terminated polysiloxanes                                              Amino terminated polysiloxanes                                                Epoxy terminated polysiloxanes                                                Carbirol terminated polysiloxanes                                             Polysilanes                                                                   1 #STR1##                                                                     Glycols                                                                       Polyethylene glycol                                                           Poly(ethylene glycol) tetrahydrofurfuryl ether                                Poly(ethylene glycol) bis (carboxymethyl) ether                               3.6.9 - trioxadecanoic acid                                                   3.6.9 - trioxaundecanedioic acid                                              Polyglycol diacid                                                             ______________________________________                                    

What is claimed is:
 1. A method comprising:forming an admixture of asolvent, a siloxane and a polymer selected from the group consisting ofa precursor to an electrically conductive polyaniline and anelectrically conductive polyaniline; said additive provides localmobility to said polymer to allow said polymer to associate with oneanother to achieve a crystalline state; and removing or partly removingsaid solvent substantially leaving said siloxane therein, said siloxaneprovides local mobility to said polymer to achieve said crystallinestate.
 2. A method comprising:providing solution of polymers in asolvent; said polymers are selected from the group consisting ofprecursors to electrically conductive polyaniline and electricallyconductive polyaniline; providing mobility to said polymers to allowsaid polymers to associate with one another to achieve a crystallinestate by adding a siloxane to said solvent.